CN113861332A - Photoresist resin and polymerization method thereof - Google Patents

Photoresist resin and polymerization method thereof Download PDF

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Publication number
CN113861332A
CN113861332A CN202111157883.3A CN202111157883A CN113861332A CN 113861332 A CN113861332 A CN 113861332A CN 202111157883 A CN202111157883 A CN 202111157883A CN 113861332 A CN113861332 A CN 113861332A
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photoresist resin
reaction
polymerizing
chain transfer
transfer agent
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CN113861332B (en
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陈鹏
卢汉林
陈情丽
马潇
顾大公
毛智彪
许从应
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Ningbo Nata Opto Electronic Material Co Ltd
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Ningbo Nata Opto Electronic Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymerisation Methods In General (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention is suitable for the technical field of photoresist, and provides photoresist resin and a polymerization method thereof, wherein the method comprises the following steps: s1, dissolving a methacrylic acid monomer and a chain transfer agent in an organic solvent to obtain a mixed solution; s2, placing the mixed solution in a protective gas environment60Carrying out polymerization reaction in a Co radiation chamber, and after the reaction is finished, putting the reaction solution into normal hexane for precipitation treatment; and S3, carrying out vacuum drying treatment on the solid after the precipitation treatment to obtain the photoresist resin. The invention mixes methacrylic monomers with chain transfer agent and adopts radiation method to lead the methacrylic acid to beThe acid monomer is subjected to polymerization reaction, so that the technical problems of high cost and low efficiency in the preparation of the photoresist resin in the prior art are solved, the yield of the photoresist resin is improved, and the polymerization condition in the preparation process is controllable.

Description

Photoresist resin and polymerization method thereof
Technical Field
The invention belongs to the technical field of high polymer polymerization, and particularly relates to a photoresist resin and a polymerization method thereof.
Background
Photoresist is a photosensitive material and is a key processing material in the fine processing technology of integrated circuits. With the miniaturization and increasing integration of electronic devices, modern lithography technology continues to advance from g-line lithography technology up to 157nm lithography technology. In order to achieve higher integration, photoresist resins require better resolution and better etch resistance. It has been found that, in order to satisfy the above characteristics, it is closely related to the molecular size in addition to the molecular groups attached to the resist resin.
Among Arf photoresists, methacrylic resins have been widely studied due to their high transparency. In order to meet the characteristics of the photoresist, a series of functional groups such as acid sensitive groups, etching resistant groups, photosensitive groups and the like are grafted on the basis of methacrylic resin. It is also necessary to control the degree of polymerization of the methacrylic resin, i.e., to be able to produce a suitably controlled molecular weight.
In the traditional process, in the process of preparing the photoresist resin, a monomer, an initiator and a chain transfer agent are added into a solution or an emulsion, and long-time polymerization reaction is carried out under the condition of heating, so that the methacrylic resin with the required molecular weight can be obtained. However, this process is difficult to control in the early stage of the reaction due to the long induction time of the initiator and the inevitable chain-extending chain termination, and may produce a large amount of short-chain polymer, which needs to be purified in the later stage. Although a proper amount of the chain transfer agent can be improved to form a long-chain and narrow-distribution photoresist resin, the amount of the chain transfer agent is increased, most of the chain transfer agents have complicated structures and are difficult to synthesize, so that the cost is wasted, and the polymerization time is required to be more than 12 hours.
Disclosure of Invention
The embodiment of the invention provides a polymerization method of photoresist resin, aiming at solving the technical problems of higher cost and lower efficiency in the prior art for preparing the photoresist resin.
The embodiment of the invention is realized in such a way that the method for polymerizing the photoresist resin comprises the following steps:
s1, dissolving a methacrylic acid monomer and a chain transfer agent in an organic solvent to obtain a mixed solution;
s2, placing the mixed solution in a protective gas environment60Carrying out polymerization reaction in a Co radiation chamber, and after the reaction is finished, putting the reaction solution into normal hexane for precipitation treatment;
and S3, carrying out vacuum drying treatment on the solid after the precipitation treatment to obtain the photoresist resin.
Preferably, in the method for polymerizing a photoresist resin, the methacrylic acid is one or more of methyl methacrylate, butyrolactone methacrylate, 2-methyl-2-adamantyl methacrylate.
Preferably, in the polymerization method of the photoresist resin, the organic solvent is one or more of tetrahydrofuran, butanone, ethyl acetate and butyl acetate.
Preferably, in the method for polymerizing a photoresist resin, the chain transfer agent is one or more of trithiocarbonate, isobutyronitrile ester of α -dithionaphthoic acid, dodecyl mercaptan, and dithiocarbamate.
Preferably, in the polymerization method of the photoresist resin, the polymerization temperature is 20 to 30 ℃.
Preferably, in the method of polymerizing a photoresist resin, the shielding gas is nitrogen.
Preferably, in the method for polymerizing a photoresist resin, the chain transfer agent is used in an amount of 1 to 5% by mass based on the monomer of methacrylic acid.
Preferably, in the polymerization method of the photoresist resin,60the radiation intensity in the Co radiation chamber is 0.5-2.5 kGy/h.
Preferably, in the polymerization method of the photoresist resin,60the irradiation time in the Co irradiation chamber is 3-8 h.
The invention also provides a photoresist resin prepared by the polymerization method of any one of the photoresist resins.
The embodiment of the invention discloses a photoresist resin and a polymerization method thereof, wherein the method comprises the following steps: dissolving a methacrylic acid monomer and a chain transfer agent in an organic solvent to obtain a mixed solution; placing the mixed solution in a 60Co radiation chamber under a protective gas environment for polymerization reaction, and after the reaction is finished, placing the reaction solution in n-hexane for precipitation treatment; and carrying out vacuum drying treatment on the solid after the precipitation treatment to obtain the photoresist resin. According to the invention, after the methacrylic monomer is mixed with the chain transfer agent, the methacrylic monomer is subjected to polymerization reaction by adopting a radiation method, an initiator does not need to be added into a polymerization reaction liquid, the technical problems of high cost and low efficiency in the preparation of the photoresist resin in the prior art are solved, the use of the chain transfer agent is reduced, the yield of the photoresist resin is improved, and the molecular weight of the polymer is controllable in the preparation process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the polymerization process of the photoresist resin, the methacrylic monomer and the chain transfer agent are mixed, and then the radiation method is adopted to carry out polymerization reaction on the methacrylic monomer and regulate and control the molecular weight of the methacrylic photoresist resin, so that the technical problems of high cost and low efficiency in the prior art for preparing the photoresist resin are solved, the yield of the photoresist resin is improved, and the polymerization condition in the preparation process is controllable.
Wherein the methacrylic acid is one or more of methyl methacrylate, methyl methacrylate butyrolactone and 2-methyl-2-adamantyl methacrylate.
Preferably, the methacrylic acid is prepared from methyl methacrylate, butyrolactone methacrylate and 2-methyl-2-adamantyl methacrylate in a mass ratio of (1-10): (1-10): (1-10) mixing.
Preferably, the organic solvent is one or more of tetrahydrofuran, butanone, ethyl acetate and butyl acetate; the chain transfer agent is one or more of trithiocarbonate, alpha-dithionaphthoic acid isobutyronitrile ester, dodecyl mercaptan and dithiocarbamate. Wherein the purpose of the organic solvent is to form a uniform mixed system of substances participating in the reaction. In addition, the amount of chain transfer agent used is 1-5% of the total mass of the monomers. The amount of the organic solvent used for dissolving the monomers is 4 to 10 times of the total mass of the monomers.
Wherein the protective gas is nitrogen, and the temperature of the polymerization reaction is 20-30 ℃, preferably 25 ℃; the dosage of the chain transfer agent is 1-5% of the monomer mass of methacrylic acid;60the radiation intensity in the Co radiation chamber is 0.5-2.5kGy/h, and the radiation time is 3-8 h.
Example 1
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 1% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60And (3) in a Co radiation chamber, regulating and controlling the radiation intensity and the radiation time to carry out polymerization reaction, wherein the radiation intensity is 0.5kGy/h, and the radiation time is 3 h. After the polymerization reaction, the reaction solution is added into n-hexane solution for precipitation treatment, wherein the usage amount of n-hexane is10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 2
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 1% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60And (3) in a Co radiation chamber, regulating and controlling the radiation intensity and the radiation time to carry out polymerization reaction, wherein the radiation intensity is 0.5kGy/h, and the radiation time is 5 h. After the polymerization reaction, pumping the reaction solution into a normal hexane solution for precipitation treatment, wherein the usage amount of the normal hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 3
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 1% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60In a Co radiation chamber, the radiation intensity and the radiation time are regulated and controlledCarrying out polymerization reaction, wherein the radiation intensity is 0.5kGy/h, the radiation time is 8h, and after the polymerization reaction, pumping the reaction solution into a normal hexane solution for precipitation treatment, wherein the using amount of the normal hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 4
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 3% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60In a Co radiation chamber, regulating and controlling radiation intensity and radiation time to carry out polymerization reaction, wherein the radiation intensity is 1.5kGy/h, the radiation time is 3h, after the polymerization reaction, the reaction solution is injected into n-hexane solution for precipitation treatment, and the using amount of n-hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 5
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 3% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60In a Co radiation chamber, regulating and controlling radiation intensity and radiation time to carry out polymerization reaction, wherein the radiation intensity is 1.5kGy/h, the radiation time is 5h, after the polymerization reaction, the reaction solution is injected into n-hexane solution for precipitation treatment, and the using amount of n-hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 6
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 3% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60In a Co radiation chamber, regulating and controlling radiation intensity and radiation time to carry out polymerization reaction, wherein the radiation intensity is 1.5kGy/h, the radiation time is 8h, after the polymerization reaction, the reaction solution is injected into n-hexane solution for precipitation treatment, and the using amount of n-hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 7
The present embodiment provides a method for polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 5% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60In a Co radiation chamber, regulating and controlling radiation intensity and radiation time to carry out polymerization reaction, wherein the radiation intensity is 2.5kGy/h, the radiation time is 3h, after the polymerization reaction, the reaction solution is injected into n-hexane solution for precipitation treatment, and the using amount of n-hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 8
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 5% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60In a Co radiation chamber, regulating and controlling radiation intensity and radiation time to carry out polymerization reaction, wherein the radiation intensity is 2.5kGy/h, the radiation time is 5h, after the polymerization reaction, the reaction solution is injected into n-hexane solution for precipitation treatment, and the using amount of n-hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Example 9
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, and stirring until the dithiocarbamate is dissolved, wherein the use amount of the chain transfer agent is 5% of the total mass of the monomer;
placing the four-neck flask containing the reaction solution at normal temperature, namely 25 ℃ at60In a Co radiation chamber, regulating and controlling radiation intensity and radiation time to carry out polymerization reaction, wherein the radiation intensity is 2.5kGy/h, the radiation time is 8h, after the polymerization reaction, the reaction solution is injected into n-hexane solution for precipitation treatment, and the using amount of n-hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Comparative example 1
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomers are dissolved, adding dithiocarbamate and azodiisobutyronitrile, stirring until the monomers are dissolved, wherein the using amount of the chain transfer agent is 5% of the total mass of the monomers, and the using amount of the initiator is 1% of the total mass of the monomers;
placing a four-neck flask containing reaction liquid in an oil bath pot with a magnetic stirrer, installing a condenser pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to the boiling point temperature of the solvent, about 66 ℃, recording the temperature and carrying out free radical polymerization reaction for 20 hours after boiling phenomenon occurs; after the polymerization reaction, pumping the reaction solution into a normal hexane solution for precipitation treatment, wherein the usage amount of the normal hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Comparative example 2
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomer is dissolved, adding dithiocarbamate, stirring until the monomer is dissolved, wherein the using amount of the chain transfer agent is 5% of the total mass of the monomer;
placing a four-neck flask containing reaction liquid in an oil bath pot with a magnetic stirrer, installing a condenser pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to the boiling point temperature of the solvent, about 66 ℃, recording the temperature and carrying out free radical polymerization reaction for 20 hours after boiling phenomenon occurs; after the polymerization reaction, pumping the reaction solution into a normal hexane solution for precipitation treatment, wherein the usage amount of the normal hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
Comparative example 3
A method of polymerizing a photoresist resin, the method comprising:
putting 3 parts of methyl methacrylate, 2 parts of butyrolactone methacrylate and 5 parts of 2-methyl-2-adamantyl methacrylate into a four-neck flask containing a tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed, wherein the total using amount of the tetrahydrofuran solvent for dissolving the monomers is 6 times of the total mass of the monomers;
after the monomers are dissolved, adding azobisisobutyronitrile, stirring until the monomers are dissolved, wherein the using amount of the initiator is 1 percent of the total mass of the monomers;
placing a four-neck flask containing reaction liquid in an oil bath pot with a magnetic stirrer, installing a condenser pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to the boiling point temperature of the solvent, about 66 ℃, recording the temperature and carrying out free radical polymerization reaction for 20 hours after boiling phenomenon occurs; after the polymerization reaction, pumping the reaction solution into a normal hexane solution for precipitation treatment, wherein the usage amount of the normal hexane is 10 times of the mass of the reaction solution;
after solid-liquid separation and drying at 95 ℃ in a vacuum atmosphere, the polymer was weighed and its GPC was measured.
The results of the tests in examples 1-6 and comparative examples 1-3 are given in table 1 below:
TABLE 1 polymerization results
Figure BDA0003288984450000091
Figure BDA0003288984450000101
As can be seen from Table 1, in comparative examples 1, 2 and 3, the chain transfer agent and the initiator need to be used simultaneously in the polymerization reaction, and if the initiator is not present, the concentration of the active free radical is too low and the polymerization is not substantially carried out; in contrast, if there is no chain transfer agent, only the initiator causes chain-lengthening chain termination reaction, so that more small-chain polymers appear in the reaction system, resulting in wider molecular weight distribution, therefore, in the prior art, the chain transfer agent and the initiator need to be used simultaneously, and a certain amount of heat is provided, so as to promote the polymerization reaction of the resin monomer.
In the examples 1 to 6, the overall reaction time is short, the yield is over 50%, and the reaction is carried out at room temperature, i.e., under the action of radiation, so that the reaction time can be greatly reduced, side reaction caused by the initiator can be avoided, and the polymerization efficiency can be improved.
Specifically, as in examples 1 to 3, the same radiation intensity, the longer the time, the reaction continued to proceed, the molecular weight increased continuously, and then the molecular weight distribution decreased first, specifically because the concentration of radicals in the reaction solution was too high with the lapse of the reaction time, slightly biased toward the chain termination reaction; the higher the radiation intensity, the more favorable the reaction is.
The polymerization method of the photoresist resin utilizes the radiation method and the chain transfer agent method to carry out the polymerization of the photoresist resin, does not need to add an initiator into a polymerization reaction liquid, solves the technical problems of higher cost and lower efficiency of the preparation of the photoresist resin in the prior art, reduces the use of the chain transfer agent, improves the yield of the photoresist resin, and simultaneously has controllable polymer molecular weight in the preparation process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A method of polymerizing a photoresist resin, comprising the steps of:
s1, dissolving a methacrylic acid monomer and a chain transfer agent in an organic solvent to obtain a mixed solution;
s2, placing the mixed solution in a protective gas environment60Carrying out polymerization reaction in a Co radiation chamber, and after the reaction is finished, putting the reaction solution into normal hexane for precipitation treatment;
and S3, carrying out vacuum drying treatment on the solid after the precipitation treatment to obtain the photoresist resin.
2. The method of polymerizing a resist resin according to claim 1, wherein the methacrylic acid is one or more of methyl methacrylate, butyrolactone methacrylate, 2-methyl-2-adamantyl methacrylate.
3. The method for polymerizing a resist resin according to claim 1, wherein the organic solvent is one or more of tetrahydrofuran, methyl ethyl ketone, ethyl acetate, and butyl acetate.
4. The method of claim 1, wherein the chain transfer agent is one or more of trithiocarbonate, isobutyronitrile α -dithionaphthoate, dodecyl mercaptan, and dithiocarbamate.
5. The method for polymerizing a resist resin according to claim 1, wherein the temperature of the polymerization reaction is 20 to 30 ℃.
6. The method of claim 1, wherein the shielding gas is nitrogen.
7. The method of claim 1, wherein the amount of the chain transfer agent is 1-5% by mass based on the monomer of methacrylic acid.
8. The method of polymerizing a resist resin according to claim 1,60the radiation intensity in the Co radiation chamber is 0.5-2.5 kGy/h.
9. The method of polymerizing a resist resin according to claim 1,60the irradiation time in the Co irradiation chamber is 3-8 h.
10. A photoresist resin prepared by the polymerization method of the photoresist resin according to any one of claims 1 to 9.
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